Organic alkaline earth metal complexes and methods of making same



Patented Nov. 4, 1952 2,616,905 ORGANIC ALKALINE EARTH METAL COM- PLEXES AND METHODS OF MAKING SAME Peter A. Asseff, Thomas W. Mastin, and Alan Rhodes, Cleveland, Ohio, assignors to The Lubrizol Corporation, Wickliffe, Ohio, a corporation of Ohio No Drawing. Application March 13, 1952,

Serial No. 276,462

20 Claims. 1

This application is a continuation-in-part of co-pending applications Ser. No. 216,101, filed March 16, 1951; Ser. No. 216,102, filedMarch 16, 1951; Ser. No. 216,103, filed March 16, 1951; Ser. No. 224,458, filed May 3, 1951; Ser. No. 263,961, filed December 28, 1951; Ser. No. 263,962, filed December 28, 1951; and Ser. No. 263,963, filed December28, 1951. V

This invention relates to organic metal complexes and novel methods for the production of such complexes.

, It is now well known that when preparing a salt or soap of an organic acid, the mere use of an excess of neutralizing agent, which in the prior art has been in the form of the oxide, hydroxide,

carbonate, etc. of the desired metal, may result in a product which contains an amount of metal in excess of that theoretically required to replace the acidic hydrogens of the organic acid used as the starting material. Work with this type of product has shown that for many uses, particularly where extreme care must be exercised to prevent the composition from being corrosive, as for example in lubricants, de-

sirable results are secured by the use of these organic metal complexes.

Materials containing an excess amount of metal prepared by earlier workers in the art can be divided into three types. In the first type, an

excess of alkali was cooked into the mixture. This can be illustrated by the McNab Patent No.

2,418,894. In the second type, illustrated by patents to Griesinger No. 2,402,325, Campbell et al.

No. 2,485,861, and Mertes No. 2,50l,731,"the excess'metal was held in solution by colloidal suspension. A peptizing agent, such as a sulfonate, was employed to peptize a metal hydroxide or carbonate.- In the third type, illustrated by the patents to McLennan Nos. 2,417,428 to 2,417,433, oil-insoluble metal complexes were prepared by complexing a high molecular weight soap with either a normally oil-insoluble organic. salt or molecularly equivalent proportions of an oil-insolubleorganic salt and an oil-insoluble inorganic salt. McLennan sought to produce an'ins'oluble lattice to aid in thickening oils to producegreases. All of his specific compositions and working examples are greases.

In the present invention it has been found that a fully oil-soluble organic metal complex can be produced with a high metal content by complexing an oil-soluble salt (hereinafter for convenience referred to as an oil-salt) with a combination, in certain critical proportions, of normally oil-insoluble organic and inorganic salts (hereinafter for convenience referred to as aqua-salts).

It is a principal object of the invention to pro vide oil-soluble metal complexes, and processes for preparing the same, of the type referred to above. i

It is understood for the purpose of the specification and claims that the term oilsalt refersto an oil-soluble alkaline earth metal salt of an organic acid. The term aquasalt refers to oil-insoluble alkaline earth metal salt. For a more detailed definition and explanation of oilsalts and aquasalts, see the sections, infra, entitled, Acids Useful in Preparation of Oilsalts, Materials Useful in Preparation of Organic Aquasalts, and The Initial Inorganic Aquasalt Used in the Process.

For the purpose of the present specification and claims, the ratio of total equivalents of metal in the complex to equivalents of oilsalt therein will be referred to as the metal ratio.

Broadly stated the invention comprises an oilsolubleorganic alkaline earth metal complex which has in chemical combination at least one oilsalt and a plurality of aquasalts; said aquasalts consisting of at least one organic aquasalt derived from salt-forming compounds having an ionization constant in water of at least 1 l0- at 25 C., water-solubilities of at least about 0.0005% at 50 C., and saturated aqueous solutions of which at about 25 C. exhibit a pH of less than 7; and at least one inorganic aquasalt,

the amount of said inorganic aquasalt present in strontium, barium and calcium and whichdoes not include magnesium or radium. By use of a single empirical formula the plexes of the present invention can be represented as follows:

Q-MAAO) MAI); wherein:

one salt-forming compound having an ioniza- 1 tion constant in water of at least 1X10 at 25 C., a water-solubility of at least about 0.0005% at 50 C., and saturated solution of; which at about 25 C. exhibit a pH of less than 7 -AI=one hydrogen equivalent of the anion of at least one inorganic aquasalt;

z=the total number of equivalents of metal in the complex;

r=the total numberof equivalents of A0 in the complex;

com- 1 y=the total :number of .equivalents :of AI .in the complex;.

and in which z=w+y+1, and the ratio is substantially greater than 1.'

There are various processes which may be uti lized to produce the complexes comprisingi'our invention as defined above. One'process whi'ch may be so utilized for this purpose may be defined as the process .for preparing a substantially-en tirely oil-soluble organic alkaline earth metal complex which comprises:

I. Mixing one hydrogen equivalent of an organic acid compound. with:

(a) I From 0.1.to 101. equivalent .ofllowlmolece ular weight. organic. salt-forming. com: poundhavingz.

(1) An ionization constant in waterloiat .1

least about 1 X 107 at .253 C.;

(2) A water solubility at-.50". C..of.;at.

least about 0;0005%; and- (3).- In saturated aqueous ..solutions.-.at;

about -'C. a pH ofless than :7;

(b) An amount of an alkaline earth .metalbase in substantial. excess of. twicethe numberof hydrogen equivalents of said. low molecularweight organic salt forming compound used; and

(c) At least-0.5- mole of :water, includingany water of hydration in .(a) and lb),

II. Heating the mass for such time-.and'temperature as to remove substantially all the-water. present,

III. Treating the masswithat least one inor-- ganic acid reagent in an .amount 'suflicient .to. neutralize at least at-portion-ot-the titratable, basicity of the mass.=

Various specific embodiments of theprocess as broadlyfdefi'nedabove are; illustrated by specificexamples in" our aforesaid .copending application" Serial Nos. 216,101-3; 224,458; 263,961 -3; Still. anotherprocess by which these complexes-may be'producedis disclosed in and forms the;sub-' ject matter of our copending application;

In one pair of experiments; a .comparisonwas made betweenxa process capable-"of :producinf-irzv a complex of thepresent invention; Examplel, and. a representative prior. art.process;:.EXample"2,; using duplicate amounts. of.:components.- It is evident from the following examples". that; this inventionwill give substantially betterresultswith respect to metal concentrationof the complex than is obtainable by conventional techniques. It is alsoapparentthat'the complex of this invention has a difierent chemical structure; than the structure of conventional metal comp EXAMPLE 1 1530'gramsof a oil.solution::ofibarium. petroleum sulphonate having a 7.6:%l: sulphate ash, 88 grams. of para-tertiary butyl phenol (ratio .of'equivalents is 1.7), 271 grams of BaO and725ml; of Water. were'mixedntogether. at SO -70C; The temperature .of'th'e "mixture was raised to .100-105'C. andheld therefor one hour while insuring thorough mixing. Thereafterthe temperature was raised to 150-160 C.'.and held at that level to remove substantially all the waterm The complex was separated byfiltration: and had the following analyses:

Basic No. 85.2 Per cent sulphate ash 25.5 Metal ratio e 4.12

Empirical formula QM4.12(AO)0.59(A1)2.53 7';

ent invention.

4 EXAMPLEaZv 1530 grams ofa 30% oil'solution ofbarium petroleum sulphonate having a 7.6% sulphate ash were mixed with 725 ml. of water at about -C.- Tli'en-271 grams of BaO were added. The

BasicNo. 36.0 Per cent sulphate ash 15.34 Metalratio 2.14

This product. made essentially, according ,to. the

teaching. of? Mertes. 2,501,731; contained. only,

, ab'out halfthe equivalent amount of Zmet'al 'asour. product Example .1.

Bye. largenumberof specific examples .we..willl illustrate various methods of preparationand examplesof complexes which comprise .the pres- EXAMPLE 3 1000 gram-s ct the barium salt ofunsaturated paraffin waxsulphonicacid containing 1311 sulphate ash were-mixed with 455 grams of-a- I mineral oil having a viscosity-M 160 SSU -'a't-'-100"' and 84.5 grams =of 'para tertiary butyl phenol- (ratio of equivalents is 20) placed in a suitablevessel and heated 'to about C; with stirring.

To this mixture was added a slurryofbarium oxide (containing 269 grams ofba-rium oxide and" 920 gramsofwater) and the total mixturewas heated at about- 'C; for *onehour: The-tem perature' was-slowly raised "to about C. and held therefor-about one-hour until substantially all of the water WES-IBIIIOVBCI. Then=about 3%- Hyflo (a filter-aid) was added-to the'producbto facilitate filtering: The salt-'complexwas'then separated by filtration; The salt comple-x' thus prepared had the following properties:

Thesalt.complexlproduct .was fiuid-,. .brown in. color, ancLdid .noticontain anyodor.

EXAMPLE 4 1000' grams ofthebarium salt of monoeparaflin wax substituted naphthalenesulphonic acid containing 8.63% sulphate ash weremixed with 445 grams of mineral oil having a viscosity of SSU at 100 F.- and 5416 gramsof para-tertiarybutyl phenol (ratio of equivalents-is 2. 0-)- andheated to about'90 CI-' A-sl-urry-of barium oxide- (203.5 grams of barium -oxide= and 543 grams of water) was added; and' the mixture was heated hour.

the salt complex was recovered by filtration. The salt complex contained the following properties:

400 grams of the barium salt of mono-paraffin wax substituted naphthalene sulphonic acid disulphide containing 8.2% sulphate ash and 27 grams of para-tertiary-butyl phenol were placed in a suitable vessel and heated to 90 C. (ratio of equivalents is 1.54). A barium oxide slurry constituting 66.5 grams of barium oxide and 180 cc. of water was added to the mixture and refluxed for about one hour. The temperature was then slowly raised to about 160 C. over a period of about four hours and held at that level for about 1.5 hours until substantially all of the water was removed. The salt complex was separated by filtering. The product was a viscous liquid, black in color, and contained a very slight'odor. The following properties were determined for the salt complex:

Basic No. 69.7

Per cent sulphate ash 24.3

Metal ratio 3.50

Empirical formula QM3.5(AO) o.s5(AI) 1.85

EXAMPLE 6 6000 grams of a 30% by weight oil solution of barium petroleum sulphonate (sulphate ash content 7.6%) were mixed with 348 grams of paratertiary-butyl phenol in a l2-liter, 3-neck flask (ratio of equivalents 1.7) and heated to 95 C. A slurry of barium oxide constituting 1,100 grams of barium oxide and 2,911 grams of water was then added and the mixture held there for about one hour at a temperature of about 90-95 C. The total mixture was then slowly raised in temperature to 150 C. and dehydrated at that temperature over a period of about 4 /2 hours. The salt complex was separated by filtration and was found to be a slightly viscous liquid, black in color, and did not contain any odor. The properties of the salt complex were as follows:

Basic No 72.1

Per cent sulphate ash 23.1

Metal ratio 3.59

Empirical formula Q1VI3.59(AO)0.59(AI)2.0

EXAMPLE 7 6 EXAMPLE 8 777 grams of di-(Z-ethyl'hexyl) dithiophosphoric acid, 308 grams of iso-nonyl phenol (ratio of equivalents 1.52) and 914 grams of solvent extracted Mid-Continent oil having a viscosity of 160 SUS 100 F. were mixed together, followed by an addition of BaO slurry consisting of 773 grams of BaO and 2,060 cc. of H20, while keeping one hour.

the temperature below 65 C. The total mixture was then heated at 100 C. for one hour, followed by a raise in temperature to 150 C. over a period of 2 /2. hours, and maintained at that level for odor. The product had the following properties:

Basic No. 78.0

Per cent barium 22.7

Per cent sulphate ash 38.6 (calculated from metal content) Metal ratio 4.52

Empirical formula QM4.52(AO)0.65a(AI)3.86

EXAMPLE 9 172 grams of di-(n-hexyl) dithiophosphoric acid, 500 grams of petroleum sulphonic acid, 159 grams of iso-nonyl phenol (ratio of equivalents of oil soluble acids to iso-nonyl phenol is 1.52), and 1,170 .cc. of water were mixed together, then .437 grams of BaO were added over a period of /2 hour. The mixture was heated at reflux temperature for 1 hour, followed by heating to 150 C. over a period of 2 /2 hours, and then maintaining that temperature for 1 hour.

The following properties were determined:

172 grams of di-(n-hexyl) dithiophosphoric acid, 500 grams of petroleum sulphonic acid and g 98 grams of para-tertiary-butyl phenol (ratio of equivalents of oil soluble acids to para-tertiary- 405, grams of di-(Z-ethyl hexyl) dlthiophosphoric acid, 99 grams of para-tertiary-butyl phenol (ratio of equivalents 1.52) and 473 grams of solvent extracted Mid-Continent oil having a viscosity of 160 SUS 100 F. were mixed together and heated to C. A slurry comprising 387 grams of BaO and 1,030 cc. of water was added quickly, maintaining the temperature at about C. The mixture was then heated to C. and held there for one hour. Then the temperature was raised to 150 C. over a period of 2 /2 hours and held there for one hour. The product was obtained by filtering the mass and was' found to be a slightly viscous liquid, red in color, and contained a slight odor. Th following properties were determined for the product:

Empirical formula QM3.65(AO) 0.658(AI) 1.99

;;butyl phenol is 1.52) were mixed together. To this mixture was added a slurry of 387 grams of BaO and 1,080 cc. of water. The mixture was heated at 100 C. forone hour, and then the temperature was raised to 150 C. and held at that level for one hour. The product was a highly viscous liquid, fbrown in color, and contained a slight odor. The

.- following properties of the product was deter- EXAMPLE 11 249 grams of petroleum naphthenic acid, 88.6

grams of para-tertiary butyl phenol (ratio of equivalents is 1.70), 1212 grams of a conven- .tionally-refined Mid-Continent oil having a viscosity of SUS 100 F., 347 grams of BaO, and 700 ml. of H20 were placed in a 5 liter, 3

neck flask and heated to 100 C. with stirring. The mixture was held at 100-105 C. for 1 hour,

and then the temperature was raised to -160 The desired product was a slightly .viscous liquid, red in color, and contained a slight The desired, product was a viscous liquid, brown in color, and contained a slight odor.

7;" C. After holding theitemperature for 1 hour at 1509-160" 0., themixture was .blown with CO2 for; 4: hour. keeping the temperature. at about 150;160?"'C. The mixture .was then filteredfwi-th Hypo. andjthe separated. pro duct. had the .follow-- ingmroperties;

BasiczNo; 1.98?

Ferment-sulphate ;a-sh*.' :10 I

Metalrratio: 4:10;j: Empirical .forxnula: QMrmKAOiotsiQADass-1 v A. mixture of different 'oi-lsoluble metal .sul-I phhna'tes' was treated in; accordance with: the method of the. present invention to determine what efiectif any .the two. types of 'sulphonates wouldhave-on-thequality ofthe product.- Such preparation is givenzinExample.12Joelow.

EXAMPLE .121

A mixture containing 500 grams of the barium salt of petrolatum sulphon-icacid (sulphate-ash 9I-2% 197 grams-of the barium sal-tof petroleum sulphonic acid (sulphate; ash 7.6%), and

grams of para-tertiary-butyl phenol (ratio of equivalents=ofthe sulphonates to promoteris 1154-) was heated to 95C. A slurry ot'barium oxide "constituting -123grams of barium oxide and 330gra=msof waterwas addedto the mixture. The-*tota-l mixture was refluxed for one hour at 100 Clandth'en=- the temperature was slowly raised to'lfifl C. for a=period ofone'hour to substantial-1y remove all the water; The complex Wasseparated-byfiltration and was'found to beailiquid, a-nd black'-in color; Thefollowing properties were determined:

Basic No 27.7.

Per cent sulphate ash 17.25

Metal ratio 2.41

Empirical formula QM2:41(AO)'c.s49 (A1) 0.76

whileemostpfthe examples given herein use either a neutral or normal salt of the organic acid.

as. asstarting material. to producethe high metalcontent complex, nevertheless it is contemplated for the purposes of 'thisinvention to employ the complexesiiproduced :bYgCQIIVQHtiOIIfil. techniques as :a; starting material. illustrates this .;concep t:

EXAMPLEJYBL lfifi ligrams-of a-bariumpetroleum sulphonate Bafiipomplexiobtained by dehydrating a barium petroleum'sulpli-onate; 7.6 l sulphateash, water and'iBaO"m-ixture at 150 C; for 'one hour, and producing a complex 'whichhas ab'asic number-- of -40, metal ratio-M2225 and a 16 sulphate ash) and 121 grams of di-isobutyl phenol' (ratio: of" equivalents 1.7) were combined and heated'to To this mixturegwas added 665 00.,Of-W2tt61,

followedhygar-slow addition of 175:grams of- BaO.:

The entire-mixture was then refluxed for one hour, and the temperature was raisedto 1509- C.

over. aiathreea'ho-ur period and heldthere for one hour. Prior to filteringgthe mass was blown With CO2 at a rate of316 cubic'foot/hr. for 1 hoursatr-lw'i Gia The product analyzedasiollowsz.

Basic No 8.67 Per. cent" sulphate ash 24.8" Metal. ratio 4.13 Empirical formula; QM4.13(AO)0.30(AI) 2.83

It' 'can beseen'from the sulphate ash analyses ofrthe'product andioverbased:sulphonatesmedzass:

The following example starting-r mater-lat that. there-1. was an: increase; from 'f16.'01130'24.'81in sulphate ash;v Clearly; therei fore, the conventionally overbased materials... can be used as starting materials in. the present. invention.

Other experiments. were conducted in .orderto. determine the efiect of a higher dehydration temperature in the preparation of the salt complex of the present invention. In: this: respect,

Examples 14 and: 15 below illustratethe, effect of higher-temperatures.

EXAMPLE 14 faint odor. The following properties=werede termined:

Basic No 71.5

Per cent sulphate ash.-. 24:3

Metal-ratio 3.80

Empirical formulae--- QM3.80(AO) Mas-(AI) 2.14.

EXAMPLE 20365 gra'mszof :30 ;oil' solution rof-zbariumr pe-. troleumzsulphonate? (sulphateash17.6'%) were"- mixed; with 74.51grams of phenol (1.67 ratio of .1 equivalents) andgheatedcto; 100-: A-bariumoxide. slurrycontainingw483 grams of barium 'ox ide and. 1290: ml; of .water' was: added: and :I the mixtureirefluxedislowiy for a. period Eof-;;one-:hour; at:100 C. The mixture waszthen dehydrated by heating. slowlyto: 200? C. and. maintainingrsuclr a temperature for: a .period'of about. one-half hour.

The salt complex was separated by gfiltration and was found to beanoily liquid-,1 reddish-brown in. color, and contained a slight odor. The following properties were determined for the complex:

Basic No 111.5.

Per; centv sulphate ash"... 32.8..

Metal ratio 5.56,

Empirical formula QM5'156(AO) 0.598(AI) 3.96

EXAMPLE .16

Azmixturegof- 2280..gra1ns'pf jam-1309613011; solution; of barium. petroleum"v sulphonate: (Sulphatea-ash: 7.6%) and 83:;grams of phenol (ratio of equiva} lents: is-a1;53')v was heated tov a: temperaturer'oii 60 C. 496 grams of barium: oxide and,1300'3 grams-ofzwater were added tothe abovemixturer and the temperature :was: raised to..90 '1,00 C; After holding at said temperaturef0r.10ne.hour; the temperature was raised overaperiod-of three. hours to C'. and'held at that level for one-.- half hour. The resultant :salt .complexwas fluid: in consistency and.dark':red in;:color.- The following properties .Were' determined:

Basic No 91.4

Per cent sulphate ash 26.8.

Metal ratio 4.37

Empirical formula QM4.37(AO)0.654(AI) 2.12.

EXAMPLE 17 80', grams .tertiarm-butyl benzene; was: reacted.

level for one. hour.

with 71 grams of chlorosulphonic acid at a temperature of 30-40 C. for a period of one hour. The resultant product, tertiary-butyl benzene sulphonic acid, was dissolved in a'little warm water and admixed with 1550 grams of a 30% oil solution of barium petroleum sulphonate (ratio of equivalents of sulphonate to sulfonic acid is 1.52). The mixture was heated to 90C., whereupon 284 grams of barium oxide and 760 ml. of water were added. The mixture was stirred for one hour at a temperature of 100- 102 C. The temperature was thereupon raised to 200 C. for a short period and then reduced to 150 C. and held at that level for a period of one hour. The salt complex thus obtained was an oily liquid, reddish-brown in color, and contained a faint odor. The properties of the product are as follows:

Basic N'o. 64.7

Per cent sulphate ash 27.0

Metal ratio 4.73

Empirical formula QM4.73(AO)0.654(AI)2.08 EXAMPLE 1:;

2500 grams of 30% oil solution of barium petroleum sulphonate (sulphate ash 7.6%) were admixed with 173 grams of paratertiary-butyl benzoic acid (1.68 ratio of equivalents) and heated to 95 C. 458 grams of barium oxide and 1215 grams of water were added to the mixture and the temperature was maintained at 100 C. for about one hour. Thereafter the temperature was slowly raised to 150 C. and maintained at that level for a period of one hour. The salt complex was filtered from the total mixture and was an oily liquid, brown in color and contained a faint odor. The following properties were determined:

Basic No .32.1

Per cent sulphate ash 19.1

Metal ratio 2.88

Empirical formula QM2.ss(AO)o.594(AI)1.29

EXAMPLE 19 630 grams of a 30% oil solution of barium petroleum sulphonate (7.6% sulphate ash) were admixed with 350. grams of nitroparafiin wax (ratio of equivalents is 0.59). Then 760 cc. of water was added, followed by the addition of 296 grams of BaO. For onehour the mixture was agitated at 90-100 C., whereupon the temperature was raised to 150 C. and held at that The mixture was filtered, and the complex obtained had the following properties:

Basic No 132 Per cent sulphate ash 33.3

Metal ratio 6.47

Empirical formula QMs.rz(AO)1.s9(AI)z.1s'

EXAMPLE 20 r to 150 C. over a period of 2 /2 hours and maintained at that level fora period of one hour. The product was an oily liquid, reddish-brown in color, and contained a slight odor. The following properties were determined for the product:

Basic No 78.2

Per cent sulphate ash 28.2

Metal ratio 4.60

Empirical formula QM4.60(A0)0.617(AI)2.98

EXAMPLE 21 1500 grams of a 30% oil solution of barium petroleum sulphonate having a sulfate ash of 7.6%, 93 grams of iso-propyl phenol (ratio of equivalents 1.7), and 670 grams of water were placed in a .3-liter flask and heated to 60 C. 250 grams of BaO were then added, and the temperature was allowed to rise to 100 C. The mixture was. held at 100 C. for one hour, followed by a rise in temperature to 150 C. over a two hour period, where the temperature was held for one-half hour. The total mixture was filtered, and the filtered product had the following properties:

Basic No 87.8

Per cent sulphate ash 25.95

Metal ratio 3.88

Empirical formula Q1W1L88(AO)0.59(AI)2.29

EXAMPLE 22 1140 grams of a 30% oil solution of barium petroleum sulphonate having a sulphate ash of 7.6% and grams of paratertiary-amyl phenol (ratio of equivalents 1.54) were heated to 70 C. Thereafter 600 cc. of water were added, followed by a slow addition of 227 grams of BaO. The mixture was refluxed for one hour, and then the temperature was raised to 160 C. over a period of four hours and held there for one-half hour. The product was separated by filtration, and had the following analyses:

Basic No. 85.5

Per cent sulphate ash 24.60

Metal ratio 3.96

Empirical formula QM3.9s(AO)o.ss(AI)2.s1

EXAMPLE 23 2583 grams of a 30% oil solution of barium petroleum sulphonate having a 7.6% sulphate ash, 144.2 grams of beta-naphthol (ratio of equivalents is 1.69) and 1262- ml. of water were combined and mixed thoroughly. Then 472 grams of BaO were added over a one hour period, followed by maintaining the total mixture at C. for one hour. The temperature was then raised to C, and held there for one hour. Prior to filtering the mixture, it was blown with CO2 for 75 minutes at which time the mixture was slightly basic. After filtering, the product analyzed as follows:

Basic No 4.88

Per cent sulphate ash 23.8

Metal ratio 3.90

Empirical formula QM3.90(AO)0.17(AI)2.73

EXAMPLE 24 1530 grams of a 30%.011 solution of barium petroleum sulphonate having a 7.6% sulphate ash, 129 grams of iso-nonyl phenol (ratio-of equivalents is 1.7) and 727 ml. of water were combined andthoroughly mixed. Then 271 grams of BaO' were added and the total mixture was held at 100 C for one hour. The temperature was thenraised to 150-160 C. and heldthere for one hour. Prior tofiltering, the mass was blown at about 150 C. with CO2 until the mixture was 1 I slightly basic. The filtered product analyzed as follows:

Basic No 3.9 Per cent sulphate ash 25.0 7 Metal ratio 4.17 Empirical formula QM4.17(AO).14(AI')3.03

EXAMPLE 2600 grams of a oil solution of barium petroleum sulphonate having a 7.6% sulphate ash, 215 grams of tertiary-butyl chlorophenol (ratio of equivalents is 1.7) and 1265 cc, of water were combined, followed by an addition of 459 grams of B20. The temperature of the. total mixture was raised to 100 C. and held there for one hour. Then the temperature was raised to 150 C. where it was held for one hour. Prior to filtering the mixture, it was blownfor three hours with CO2 at1-35-145 C. until the mixture was slightly basic. The filtered product analyzed as follows:

Per cent sulphate ash 2545 Metal ratio l-- z 4.33

Empirical formulaenfih. QMmfl-AO) 0.4:;(AI) m EXAMPLE 26 1530 grams of a 30% oil solution of barium petroleum sulphonate having a 7.6 sulphate ash and 131 grams. of methyl naphthalene sul- U Basic No Nil Per cent sulphate ash 25.9

Metal ratio 4.41

Empirical formula QM4.41(AO)0.59(AI)2.82 EXAMPLE 27 1530 grams of a 30% oil solution of barium petroleum sulphonate having a 7.6% sulphate .ash, 113 grams of. dii'sobutenyl sulphonic acid '(ratio of equivalents is 1.7) and 725 grams of H20 were, combined and heated to 70 C. To this mixture were added 271 grams of BaO, and the entire mixture was heated at 100 C. for one hour.

The mixture was then heated at 150 C. for one hounfollowed' by blowing with C02 at 150 C.

prior to filtering, to obtain a substantially neutral mass. The filtered product analyzed as follows:

Basic No 0.23

Per cent sulphate ash 24.6

Metal ratio 4.10 Empirical formula QM4.10.(AO) 0.55(AI) 2.51

EXAMPLE. 28

Di-isopropyl benzene sulphonic acid obtained by reacting 162 grams of di-isopropyl benzene with 122 grams ofchloro sulphonic acid for one hour at 100 C. were combined with 2600 grams of a 30% oil solution of barium petroleum sulphonate having a 7 6% sulphate ash and 1220 ml. of water. The ratio of equivalents of oil soluble sulphonate to sulphonic acid is 1.7. Then 471 grams of BaO' were added slowly and the mixture held at 100 C. for one hour. Prior to filtering,

the mixture was blown with CO2 for one half 12 hour at 120-140 C. The filtered product analyzed as follows:

Acid No 1.22

Per cent sulphate ash 25.4

Metal ratio 4.33

Empirical formula QM4.33(AO)0.59(AI)2.-.4

EXAMPLE 29 Cymene sulphonic acid obtained by reacting 134 gramsof cymene with 122' grams of chlorosulphonic acid at 70-100 C. for 1 hours were combined with 2600 grams of a 30% oil solution of barium petroleum sulphohate having a 7.6% sulphate ash and 1220 ml. of water. The ratio of equivalents of oil soluble sulphonate to sulphoni'c acid is 1.7. To this mixture was added 461 grams of BaO, and the entire mixture was then held at -100 C. for one hour. Then the temperature was raised to 150- C. and held there for one hour. Prior to filtering, the mass was blown with CO2 for one-half hour at 130 C. The filtered product analyzed as follows:

Acid No 11-1-..- 0.95

. Per cent sulphate ash 25.8

Metal ratio 4.38 Empirical formula QM4.38 (AO) 0.59(AI) 2.79

' EXAMPLE 30 Basic No. 6.45

Per cent sulphate ash 23.2

Metal ratio 3.85

Empirical formula QMlma (AO') 0.2::(AI) 2.63

EXAM LE 31 2600 grams of a. 30% all solution of barium petroleum sulphonate having a 7.6% sulphate ash, 236' grams of di-isopropyl dithiophosphoric acid (ratio of equivalents is 1.7) and 1220 ml. of water were combined, followed by a slow addition of 461 grams of BaO. The mixture was held at C. for one hour, and then heated to 150 C. and held there for one hour. Prior to filtering, the mass was blown with CO2 for 20 minutes at -450 C. The filteredproduct analyzed as follows:

Acid No 0.27

Per cent barium. 14.25

Per cent sulphate ash... 24.2 (calculated from metal content) Metal ratio 4.15 Empirical formula QM4.rs(AO)o;s9'(AI)'-2;s6

EXAMPLE 32 25 80gr'ams of a 30% oil solution of barium petroleum sulphonatehaving a 7.6% sulphate ash, 99 grams of acetyl-acetone (ratio of equivalents is 1.7) and 1260' cc. of water were combined, followed by a slowjaddition of 455 grams of BaO over a one hour period. The entire mixture was heldat 94 C. for one hour, followed by a one hour period of heating at C. Prior 'to filtering, the mass was blown with CO2 for one in ,color, and contained a mild odor. .jng properties were Basic No 3.2

filtered product ana- Per cent sulphate ash 22.7

Metal ratio 3.48

Empirical formula QM3.48(AO)0.10(AI)2.38

' EXAMPLE 33 1530 grams of a 30% oil solution of barium petroleum sulphonate having a 7.6% sulphate ash and 206 grams of di-t-butyl naphthalene sulphonic acid (ratio of equivalents is 1.7) were combined and heated to 70 C. 725 grams of water were then added, followed by, a slow addition of 271 grams of BaO. The mixture was refluxed for one hour, and then held at 150 C. for one hour. Prior to filtering, the mixture was blown with CO2 at a rate of 3.6 cu. ft./hr. for 1.25 hours at a. temperatur of 150 C. The filtered product analyzed as follows:

Acid,N l 0.24

Percent sulphate ash- 23.6

Metal'ra'tio 4.12 Empirical formula QM4.12(AO)0.59(AI)2.53

The salt complex can also be prepared by starting with the oil-soluble sulphonic acid and treating with an organic salt forming compound from which the organic aquasalt is derived and the inorganic metal compound. This technique differs from those given above because as shown in all the above examples, the normal metal sulphonate or conventionally overbased sulphonate was employed as a starting material. In order to demonstrate that the metal ratio of the salt complex obtained by this method is greater than by conventional techniques, a comparison was made with a conventional technique in which the acid was employed as a starting material. In this respect, Example 34 below is illustrative.

, EXAMPLE 34- The oil-soluble petroleum 'sulphonic acid employed in this test was derived by reacting a 60% oil solution of sodium petroleum sulphonate with the ,stoichiometric amount of sulfuric acid (96% strength) at a temperature of 60-70 C.

;150 C. so as to remove substantially all of the water. The product was a viscous liquid, brown The followdetermined for the desired product:

Basic No 74.2-

Per cent sulphate ash 24.4

"Empirical formula -l ns. QM4.02(AO 0.72(AI) 2.30

.ii hejsalt complexes of the present invention ';can be prepared by first adding water to the mixture of the oil-. soluble metal sulphonate or sulphonic acid and the organic compound corre- 1.4 an alternative method bywhich the salt complex can be prepared.

EXAMPLE s5 1000 grams of the barium salt of di-paraifin wax substituted phenol sulphonic acid (sulphate ash 6.6% were admixed with 55 grams of paratertiary-butyl phenol) (ratio of equivalents is 1.54) and heated to a temperature of C. 800 cc. of waterwere then added. The mixture was mixed thoroughly and then 300 grams of dry barium oxide were added. The total mixture was refluxed for two hours followed by an addition of '573'grams of a mineraloilhaving a viscosity of 160 SUS at F. The temperature was raised over a period of four hours to 170 Cland then maintained there one hour. The salt complex was obtained by filtering the product and was found to be av viscous liquid, dark brownin color, and contained a faint odor. The following properties were determined for the salt complex:

Basic No 67.8

Per cent sulphate ash 23.8. Metal ratio .-'6.67 V EmpiricaI formula QM6'.s'1(AO)b.e5(AI)5.c-.:

Another experiment was performed in which the preformed organic aquasalt was added to'the process mass. Example 36 below illustrates this feature of the invention. 7

EXAMPLE 36 1700 grams of a 30% oil solution of barium petroleum sulphonate (sulphate ash 7.6%) were admixed with grams of barium phenate (ratio of equivalents is 1.70), and 570 grams of water. The mixture was heated to 75l00 C. whereupon 214 grams of barium oxide were added. The temperature of the mixture was maintained at 100 C. for one hour and then raised slowly to C. and held at this level'for a period of one hour. The salt complex was then separated by filtration and was found to be a viscous liquid, light brown in color, and contained a slight odor. The following properties were determined for the salt complex:

Basic No 68 Per cent sulphate ash 21.4

Metal ratio 3.23 Empirical formula- QM3.23 (AO)0.59 (AI)1.64

The following examples by comparison illustrate the substantial increase in metalcontent of the complex which is obtained by treating the mass with an acidic material before filtering to separate the desired product.

EXAMPLE 37 1700 grams of a 30% oil solution of barium petroleum sulphonate having a sulphate ash of 7.6% were mixed with 134 grams of diisobutylphenol (ratio of equivalents is 1.7) and heated to 70 C. 302 grams of BaO and 800 cc. of water were added thereto, and the mixture was refluxed for one hour. The temperature was then raised to C. over a period of 6 hours and maintained at that temperature for one hour. The mass was filtered and the product obtained was a liquid, brown in color, and contained a slight odor. The following properties of the products were determined:

Basic N0 66 Per cent sulphate ash 22.2

Metal ratio 3.64 Empirical formula QM3.64(AO)0.59(AI)205 ae'iepos' phenoli (ratio of equivalentsisll'l'l and heated 166.70? CI Then 800 cc. of .I-IiO andi302 grams of Ba were added'andithe mixture refluxed for one hour. The temperature was raised to 150C. and maintained there for one hour. CO2 was then injected. therethrough at. 150-'CI and at Ya. rate of "116501 cc./min. for- 38 minutes. Themass was then cooled and filtered toseparatethe complex. The product was liquid, brown in-colcr, and contained a :falntodor. The following properties of the product were determine'di BasicNo; -c 5.05:

Per. centzsulphatez'asmnl 26.0

Metal ratio--- 4.52.

Empirical formularnmma QM4 52(AO) o.'22(AI)s.ao

-- EXAMPLE 39 400 lbs. of a %v oil-solutionof'bariump'etroleum sulphonate having a sulphate ash' of 7.6% were heatedto 80*"C., and'32.'5"lbs: of'diisobutyl-phenol (ratio of equivalents is 1.67) were-added thereto. Then 19'? lbs. of waterwere added to. the'mixture,.with stirring to. insure thoroughrmixing. 73: lbs; of BaO were-added thereto over a 30 minute period at -80 C. The mixture was agitated for about 10 minutes more at C., then the "temperature was raised to C. and heldtherefor onehour. Thereafter, the temperature was raised to about-150 C. and maintained-at that-level for one hour. Follow-- ing thisstep, CO2 was blown through the mass until-about 'ls lbs. thereof hadbeenused over a. period'ofthree hours andatatemperature'of -170 C. The mass was then filtered and the product was found to I have the following prop erties:

Basic-'No 5.0

Percent sulphate ash; 25.7

Metal-ratio 4'.-35

Empirical'formula QM4.c5(AO)o;1a(AI)3.1'z

EXAMPLE 40 4590 grams of a 30% oil solution ofbarium petroleum sulphonate having a 7.8% sulphate ash, 363 grams of diisobutylephenol (ratio of equivalents is 1.7) and 2,800 grams of H20 were heated to 60 0. 1,042 grams of BaO were addedslowly and then thetemperatureofthe mixturewas raised' to 94-98 C. and held therefor one hour. Thereafter the temperature was raised to C. in four hours, and maintained there for one hour. A small portion of the mass, 361 grams, was removed and'filtered to give product a A;. whereas the remainder (5,296 grams) was blown withSOz at C. until 330 -grams'thereof waspused's. This latter mass was then fil-teredi'and the: product given' below as product B was: obtained; The-anlyses'ofproducts A andB are as follows: z

From the foregoing examples it is shown that the method of treating the mass-prior to -filtering with an acidicrmaterial results -insubstantial"in- 1.6 crease: sulphate of the tcomplex rand thus correspondingly higher metal ratios;

The salt complexes can also be prepared by combining the oil-soluble metal'sulphonate and inorganic metal compound in the presence of the sediment which forms occasionally. in some of 'the methods illustrated" above. The following examples illustrate theutilityof the sediment for preparing.salt complexes of thepresent invention.-

EXAMPLEAI.

1700 grams of a 30% oil solutionofi barium petroleum sulphonate having-'- a; 7.6% sulphate ashwere-m-ixediwith 61 grams ofsphenol (ratio of equivalents is 1.70) andithelmixturewaszheat ed to 75 C; 26l grams of'barium oxide :and: .710 grams ofwater were'then added andvtheztotal mixture was raised in temperature to .100? C. and held at-that level for one hour. Thereafter, .the temperature: was-raised" slowly. to: 150 C. and held there for aboutione hour. The total mixture was allowed to set tle overnight, followed by decantation and filtering. In this experiment 450 gramsof sediment were produced; The filtered salt complex was a viscous liquid, light brown in color, and contained a slight odor. The following properties of the product were deter mined.

Basic No l al 595 Per. cent sulphate .ash 2112.

Metal. ratio 3.20

Empirical formula QM3.20(AO) o.59(AI) 1.61

Thesediment obtained in Example' ll was emplcyed' in the preparation of a salt. complex: in the method-given in :the following Example 42'.

EXAMPLE 42 Basic -No 82.6 Percentsulphate-ash 26.4

Metal ratio. 4.66 V Empirical. formula- QM-ms (A0) 0:21(AI) 3:45

p Inn the following examples; organic acids or salts there'of and in'organic alkaline earth metal compounds containing a metal'other than barium were combined in r the presence of a promoter to produce overbased products.

EXAMPLE 43 1,120 grams of a 45% oil solutionof' calcium petroleum sulphonate having aisulphate ash content of 6.5%, 59 grams of l-nitro-propane (ratio of: equivalents: is 1. 52); 150 gramsof Ca(OH) 2 830 'mlJ ofwater were mixed' together, and heated to-aboutlw fl. for about one-hour; The temperaturewas then raised to 150 C; and held at that level for: one hour. The productwas separated by; filtering, andwas foundto be a viscou's liquid; brown in color. and contained a the following properties:

Basic No 36.1 Percent sulphate ash 13.15 Metal ratio 2.36 Empirical formula QMzsc (A) 0.18 (AI) 1.15

The following example illustrates the use of a different promoter when employing the calcium metal in the components:

EXAMPLE 44 A mixture of 459 grams of phenol, 244 grams of water, and 90.5 grams of Ca(OI-I)z was'stirred at the reflux temperature for two hours. Thereafter 1046 grams of a 45% oil solution of calcium petroleum sulphonate having a 6.7 sulphate ash content were added (the ratio of sulfonate to phenol in the mass is 0.205). The mass was then heated to 125 'C., at which temperature a distillate consisting of 244 grams of water and 32 grams of phenol was obtained. Thereafter the dehydratedmixture was blown with CO2 for 3 hours at 120-150'C., and an additional 60 grams of distillate were collected, which distillate on analysis was found to contain 42 grams of phenol. On further heating to 200 C. under 20 mm. Hg absolute pressure, 375 grams more of phenol were recovered. The residue in the flask was then filtered to separate the desired salt complex, which was a brown, odorless fluid. The salt complex had the following analysis:

Basic No 8.07 Percent sulphate ash 18.35 Metal ratio 3.07 Empirical formula QM3.0'7(AO)0.16(AI)1.91

Another'preparation w'as made in which dissimilar alkaline earth metals were present in the organic acid compound and inorganic metal compound. The following example illustrates this feature of the invention.

EXAMPLE 45 1793 grams of a 45% oil solution of calcium petroleum sulphonate having a 6.45% sulfate ash, 206 grams of octyl phenol (ratio of equivalents is 1.7) and 954 grams of water were mixed together. Then 358 grams of BaO were added, and the mixture was agitated thoroughly. While insuring thorough mixing the temperature was raised to 90-l00 C. for one hour. Thereafter, the temperature was raised to 150 C. over a two hour period and held at that level for one hour. The complex obtained by filtering the mixture had the following properties:

Basic No 4.2

Percent sulphate ash 25.2

Metal Ratio 3.94 Empirical formula QM3,94 (A0) 0.59 (AI) 2.35

The complexes of this invention can be also obtained by using a mixture of oil soluble organic acid and the alkaline earth metal salt thereof. The following example illustrates this concept.

EXAMPLE 46 and 5395 grams of water) was added and the mixture was then maintained at'a temperature of about 90-95 C. for an additional hour. Upon inspection, the mixture appeared thoroughly mixed, therefore the temperature was slowly raised to 150 C. and held there for approximately one hour. The product analyzed as follows:

Basic No 73.0

Percent sulfate ash -23.3

Metal ratio 3.73

Empirical formula QM3.13(AO)0.62(AI)2.11 EXAMPLE 1239 grams of salt complex produced in Example was heated to a temperature of 190 C. While-maintainingthis temperature for a period of 1 ,4 hours, CO2 was blown through the mixture. The temperaturewas then lowered to 150 C., continuing the passage of COzthrough the mixture, and the basic number of the mixture was tested every 10 minutes, until the analysis showed a basic number of 2.5. The salt complex- COz product was then separated and was found to be liquid in consistency, brown in color, and contained a very slight odor. The following properties were determined for the product:

Basic No. 2.5 Per cent sulphate ash 23.2

By comparison, the product of Example 35 contained a sulphate ash of 23.8% whereas the same product after blowing with CO2 contained a sulphate ash of 23.2. Therefore, it can be seen that themetal ratio of the salt complex is substantial ly the same after treatment with CO2.

Empirical formula QM6.67(AO)0.06(AI) 5.61

EXAMPLE 4s 6043 grams of the'salt complex prepared in accordance with Example 6 were placed in a suitable vessel and CO2 gas was injected at the bottom of the vessel at a rate of 3750 cc. per minute for a period of 1 V hours. During this period, the temperature was in the range of 3070 C. At the end of the blowing operation the product weighed 6346 grams, showing a gain in weight of 311 grams. The productwas fluid, dark red in color, and contained no odor. The following properties were determined for the salt complex- COzproduct: 6 I

Basic No. 4.3 Per cent sulphate ash c 22.7

It can be seen, therefore, by the gain in weight of the product that the CO2 actually enters into combination with the salt complex. Furthermore, the metal ratio of the product is substantially the same as the salt complex prior to being blown with CO2, since the sulphate ash content is substantially the same as before CO2 treatment, and conformed to the empirical formula:

QM3.59 (AO) 0.14(AI) 2.45 v

Another salt complexproduct which was blown with COzis given in Example 49 below. 7

EXAMPLE. 49

2500 grams of a 30% oil solution of barium petroleum sulphonate containing 7.6% sulphate ash were mixed with 45.6 grams of phenol (ratio of equivalents is 3.36) and heated to C. A slurry of barium oxide containing 422 grams of barium oxide and 1125 ml. of water was added to the mixture, with stirring, and held at a temperature of 97-102 C. for a period of one hour.

The temperature was then slowly raised over a period of three hours to 150 C. and maintained at that level for an additional period of one hour until substantially all the water was removed. The desired salt complex was separated by filtering and was found to be anoily liquid, brown in color, and contained a faint odor. The following properties were determined:

Basic No 60.6

Per cent sulphate ash 22.3

Metal ratio 3.34

Empirical formula -1").-. QM3.34(AO) 0.30 (AI) 2.04

EXAMPLE 50 1250 grams of the salt complex produced in accordance with the method given in Example 49 above were blown with CO2 for approximately two hours at a temperature below 60 C., until an acid number of 5.0 was obtained. The weight of product obtained was 1260 grams.

The COz-salt complex product was then heated at a temperature of 190 C. under 'a vac- Basic No. 2.96 Per cent sulphate ash 22.4

The per cent sulphate ash of the COz-salt complex product indicates that little or no metal is removed from the complex as a result of the CO2 treatment and the distillation step to recover the ionizable organic compound. The product conformed to the empirical formula:

QM3.34(AO) 0.09,(AI) 2.29

EXAMPLE 51 I440 grams of the salt complex obtained by the method given in Example was blown with CO2 for about two hours at a temperature of 30- 60 C. until the product showed an acid number of 6. The product thus obtained was then heated at a temperature of 200 C. under vacuum of 4 mm. to recover approximately 15 grams of phenol. The residue of the distillation was a viscous liquid, light brown in color, and contained a slight odor. This product possessed the following properties:

Basic No. 1.06 Per cent sulphate ash 22.6- Metal ratio 3.20 Empirical formula QM3.20(AO) 0.os(AI)2.17

Here again it is shown that the treatment of the salt complex with an acidic material liberates the promoter from complex formation.

EXAMPLE 52 6000 grams of a 30% solution of barium petroleum sulphonate (sulphate ash 7.6%), 348 grams of para-tertiary-butyl phenol (ratio of equivalents is 1.70), and 29.15 grams of water were mixed and heated to a temperature of 60 C'. 1100 grams of barium oxide were added slowly and the temperature of the total mixture was raised to 94-98 C. and held there for one hour.

20 The temperature of they mixture was then slowly raised over a period of 7 /2 hours to about 150 C. and held at that level for an additional hour until substantially all the water was removed. The salt complex obtained is a liquid, brown in color, and did not contain any odor. The following properties were determined:

Basic No 82.5

Percent sulphate ash 26.0

Metal ratio 4.2

Empirical formula QM4.2(AO) 0.59(AI) 2.61

An experiment was conducted in order to determine whether air which contains CO2 would be effective as an acidic material. The examples below illustrate the utility of air for this purpose.

EXAMPLE 53 380 lbs. of a 30% oil solution of barium petroleum sulphonate were mixed with 21.9 lbs. of para-tertiary-butyl phenol (ratio of equivalents is 1.7) and 184 lbs. of water. This mixture was heated to 50 C. and 68 lbs. of BaO were added over a period of 1 hours while not permitting the temperature to go above 65 C. The total mixture was held at C. for one hour, then heated to C. over a period of 4.8 hours and held there for one hour. The desired product was fluid, dark red, and possessed the following properties:

Basic No. m 80.5

Percent sulphate ash 2.6.0

Metal ratio 4.2

Empirical formula QM+.-z(AO)u.s9(AI)2.si

EXAMPLE 54 6000 grams of the product produced in Example 53 were placed in a 12-liter, S-necked flask and heated to C. The mass was then blown with air until a basic number of 1 was obtained. The final product contained a sulphate ash of 26.4% indicating substantially no change in the amount of metal present. The product had the empirical formula: QM3.2 (A0) 0.03 (AI) 3.17.

In all of the foregoing examples, the ratio of equivalents of the organic acid or salt thereof to the promoter has been within the preferred range, viz. 1.5-3.5 to 1. The following examples illustrate the preparation of end-products wherein the ratio of equivalents falls outside of said preferred range, but comes within the broad range found to be operable.

EXAMPLE 55 1000 grams of a 30% oil solution of barium petroleum sulphonate containing 7.6% sulphate ash were mixed with 750 grams of water at 50 C. 282 grams of 32.0 were added thereto, followed by the addition of a slurry consisting of 460 grams of water, 87 grams of BaO, and 115 grams of para-tertiary-butyl phenol (ratio of equivalents of sulphonate to phenolic compound is 0.77). The mass was stirred for one-half hour at about 100 C., then it was heated to 200 C. and maintained at that temperature for 2 hours.

The salt complex was separated by filtration. It was a red-brown, viscous liquid, and had the following properties:

Basic No 46.

Percent sulphate ash 27.9

Metal ratio 5.4

Empirical formula QM5.4(AO)1.3(AI)3.1

EXAMPLE 56 2760 grams of a 30% oil solution of barium petroleum sulphonate containing 7.6% sulphate ash were mixed with 217 grams of BaO, 580 grams of water and 41 grams of diisobutenyl sulphonic acid in that order. The ratio of equivalents of sulphonate to sulphonic acid is 9.

The mass was heated for'one hour at about 100 C., then the temperature was raised to 150 C. and maintained there for one hour. The salt complex was separated by filtration. It was a viscous, brown liquid, and had the following properties: 7

Basic No 34 Percent sulphate ash 17.3

Metal ratio 2.4

Empirical formula QM2.4(AO)0.11(AI)1.29

EXAIWPLE 57 1000 grams of petroleum sulphonic acid, 98.1 grams of para-tertiary-butyl phenol (ratio of equivalents of sulphonic acid to phenolic compound is 1.7) and 989 grams of water were mixed together and heated to 50 C. Thereafter 258 grams of strontium oxide (SrO) were added to the mixture and the temperature was raised to 100 C. and maintained at that level for about one hour. Then the temperature was raised to about 150 C. and held there for an additional hour. Thereafter CO2 was introduced into the mixture for /2 hour at a rate of 2 cubic ft. per hr. and the salt complex separated by filtration. The salt complex was a liquid of a brownish color and had the following analyses:

Basic No 1.87

Percent sulphate ash--. 13.7

Metal ratio 1.65

Empirical formula Q1\1.65(AO)0.047(AI)0.60

EXAMPLE 5:;

1530 grams of a 30% oil solution of barium petroleum sulphonate having a 7.6% sulphate ash and 210 grams of trichlorodiphenyl ether sulphonic acid (ratio of equivalentsis 1.7) were heated to 70 C. To this mixture were added725 grams of water followed by the addition of 271 grams of 32.0. The entire mixture was refluxed for one hour, then heated to 150 C, over a three hour period and held there for one hour. Prior to filtering, the mixture was blown with CO2 at 150 C. and at a rate of 3.6 cu. ft./hr. for one and one-half hours. The filtered product analyzed as follows:

Basic No 0.45

Percent sulphate ash 24.7

Metal ratio (1.34

Empirical formula QM4.34(AO)0.59(AI)2.75

It should be noted that in all of the specific examples given above, the mahogany sulphonates were referred to as either calcium, barium or strontium petroleum sulphonate, and likewise a similar designation was used for the mahogany acid.

The alkaline earth metal complexes of the-invention heretofore described can serve as starting materials for the production of metal complexes of even higher metal content, which shall be termed for convenience as superbased salts or superbased complexes.

In this particular aspect of our invention, the complex produced in accordance with the techniques previously set forth is first treated with an inorganic acidic reagent which when present in the reaction mass has an ionization constant higher than that of the organic compound whose anion is present in the organic aquasalt. Acidic reagents useful for this purpose include, for example, the strong mineral acids as well as various acid anhydrides and acid halides. Examples of suitable acidic reagents, effective in the presence of either free or combined water, include HCl, H2804, HNOa, CO2, COS, S02, S03, air (because of CO2 content), N02, HzS, HgSe, N203, P013, SOC12, SOzClz, C102, BFs, H2F2, CS2, and the like.

The choice of the particular acidic reagent to be used in connection with the superbasing technique is influenced by the type of organic aquasalt present in the initial metal salt complex starting material. salt has been formed. of a weakly acidic compound such as phenolic and enolic compounds, relatively more acidic reagents such as CO2 or COS will possess a high enough ionization constant in the reaction mass to liberate at least a portion of the anion of such compounds from their aquasalts. On the other hand, when the organic aquasalt is formed from a relatively strong acid, e.g. a carboxylic acid, the acidic reagent selected must be one which will have a higher ionization constant, i. e. a stronger acidic reaction, so as to perform the function of liberating at least a portion of the anion of such stronger acid from its aquasalt prior to the superbasing step described below.

After the "acid-treated metal complex has been prepared, the next step in our superbasing technique is to add a proportion of inorganic alkaline earth metal compound, preferably from 3 to 40% by weight, and optionally water and an additional amount of an organic aquasalt or the free salt-forming compound from which such aquasalt is formed. Thereafter the mass is heated to a temperature not substantially in excess of 350 0., preferably from about C. to 200 C., to effect the complexing of the inorganic alkaline earth compound and thereby yield the desired superbased salt.

The superbased salt may be used as such or may be treated with an additional amount of acidic reagent to reduce its titratable basicity. As a further refinement, the latter acid-treated material may be complexed with additional inorganic alkaline earth metal compound to further increase its metal content. For most purposes, however, the superbased salt initially produced will be found to be satisfactory.

The following examples illustrate the prepara-- tion of superbased salts-in accordance with the general principles which-have been set forth.

EXAMPLE 59 (a) 6000 grams of a 30% solution of barium petroleum sulphonate (sulfate ash 7.6%), 348 grams of para-tertiary butyl phenol (ratio of equivalents is 1.53), and 2911 grams of water were mixed and heated to a temperature of 60 C. 1100 grams of barium oxide were added slowly and the temperature of the total mixture was raisedto 94-98 C. and held there for one hour. The temperature of the mixture was then slowly raised over a period of 7% hours to about C. and held at that level for an additional hour, until substantially all the water was removed. The metal complex obtained is a liquid, brown in When the organic aquacolor, and did not contain any odor. The following properties were determined.

Basic No. 82.5 Percent sulfate ash 26.0 Metal ratio 4.35

(b) 6623 grams of the. metal complex produced in accordance with (a) above were treated with S02 until 327 grams. of the gas were combined with the metal complex. The product thus obtained had a neutralization number of 0. The SOs-metal complex product was Iiqui'd,,brown in color, and did not contain any odor.

(c) 1000 grams of the SO2-t'reated metal complex produced in accordance with (b) above were mixed with 286 grams of water and heated to a temperature of 60 C. Thereafter 107.5 grams. of barium oxide were added slowly and the temperature was then maintained, at 94-98" C... for one hour. Following this step, the total mixture was raised in temperature to 150 C. over a period. of 1 hours and held there for a period of one hour. The superbased salt was purified by filtration, and was found to be a liquid, brown in color, and did not contain any odor. The following properties of the superbased salt were determined:

Basic No. 38.6

Percent sulfate ash 33.7

Metal ratio 6.30

Empirical formula QMs.3(AO)o.65(AI)4.65

It can be seen from (a) above that the sulphate ash of the product increased from 26.0 to 33.7. Furthermore, the product produced in (b) above involved the treatment of complex with S02 to obtain a zero basic number; whereas in (0) above, the basic number was increased to 38.6. It is clearly shown, therefore, that by additionally treating the SOz-metal complex product with an inorganic metal compound, the resultant product contains additional metal over and above that which is found in the complex prior to treatment with the organic metal compound.

In the next example, it will be shown that water is not required in the superbasing step, in order to obtain superbased salts which contain substantially more metal than the organic salt complex starting material.

EXAMPLE 60 (a) 6000 grams of 30% oil solution of barium petroleum sulphonate, (sulfate ash 7.6%) 348 grams of para-tertiary-butyl phenol, (ratio of equivalents is 1.53) and 2911 grams of water were mixed and heated to a temperature of 60 C. To this mixture were slowly added 100 grams of barium oxide and the temperature was then raised to 94-98 C. and held there for a period of one hour. The total mixture is raised in temperature to 150 C. over a period of 7 hours and held there for a period of one hour. The metal complex is separated by filtering the product. The complex was found to be a liquid, brown in color, and did not contain any odor. The following properties were determined for the product.

Basic No. 72.8 Per cent sulfate ash 22.3 Metal ratio 3.69

(b) 6190 grams of the metal complex obtained in accordance with the method given in (a) above were treated with CO2 for a period of 1 /2 hours, at a temperature of 26-55 C. The total 24 gain in weight of the complex by virtue of the CO2 treatment was 1'79 grams. The final prodnot had a. basic number of 1.5.

(c) 1029 grams of the COz-metal complex of (b) above were heated to 50C. and then 109.8 grams of anhydrous barium hydroxide were added. The total mixture was held at a temperature of C. for one hour and the temperature was raised to 150 C. and held at that level for a period of one hour. The desired superbased salt was separated by filtering and was found to be fluid in consistency, and reddish brown in color. The following properties were with the product of (a) above, it can be seen from the sulfate ash analyses that an appreciable. amount of metal has been incorporated in the ultimate product.

EXAMPLE 61 (a) 400 lbs. of a 30% oil solution of barium petroleum sulphonate (sulfate ash 7.6%) were placed. in a. suitable vessel and heated to 26 C. At this temperature 32.5. lbs. of diisobutyl-phenol were added, and the mixture was mixed thoroughly. Then 197 lbs. of water were added, followed by an addition of 73 lbs. of BaO over a 30 minute period, while keeping the temperature at 57-84 C. Thereafter the temperature was raised to 100 C. and kept there for 1 hour, followed by another temperature increase to 152 C. and maintained at the latter level also for 1 hour. The process mixture was then blown with 75 lbs. of CO2 over a three hour period and at a temperature of -170 C. The separated product had the following properties:

Basic No. 5.0 Per cent sulfate ash 25.7 Metal ratio 4.35

Basie No 42.8

Per cent sulfate ash 33.7

Metal ratio 6.3

Empirical formula QMs.3(AO)1.ca(AI)3.s2

The remainder of the unfiltered process mass was blown with CO2 at a rate of 3 cubic feet per hour for 1 hour at C. The process mass was then filtered and the desired superbased salt had the following properties.

Basic No 7.6

Per cent sulfate ash 39.8

Metal ratio 9.3

Empirical formula QM9.3(AO).37(AI) 1.93

The above data clearly demonstrates the beneficial use of a promoter in preparing a superbased salt. Furthermore, it should be noted that upon treating the process mass, prior to C. for 1 hour.

filtering, with an acidic material, the metal content'is substantially increased asis evident from the sulfate ash analyses in the above example. Another experiment was conducted in which a different promoter was utilized in the superbasing step.

1 EXAMPLE 62 (a) 380 pounds of a 30% oil solution barium petroleum sulphonate having a 7.6% sulfate ash, 21.9 pounds of para-tertiary butyl phenol and 184 pounds of water were admixed in a suitable vessel, and then heated to 124 F. 68 pounds of BaO were added to the mixture over a 1 /2 hour period while the temperature was maintained at 124-184 F. "The temperature of the total mixture was raised to 211 F. in one hour and maintained at that level for an additional hour. Thereafter, the temperature was again raised to 308 F. over a 4.8 hour period and held at that level for 1 hour. I-Iyfio, a filter aid, was added and the material was filtered while still hot. The separated product had the following properties.

Basic No. 80.5 Per cent sulfate ash 26.0 Metal ratio 4.2

(b) 355 pounds of the metal complex of (a) above were heated to about 110 F. Then 14.5 pounds of gaseous CO2 were passed through the metal complex over a 5 hour' period, while maintaining the temperature at about 110-165 F. The treated metal complex was cooledand the following analyses were determined.

Acid No. 2.4 Per cent sulfate ash. 25.1

Metal ratio i 4.2

3000 grams of the above CO2 treated metal complex and 210 grams of paratertiary butyl phenol were mixed together and heated to 100 C. 618 grams of BaO were added to the mixture, and then the temperature was held at 100 Thereafter the temperature of the total mixture was raised to 150 C. in 70 minutes and held at that level for 3 hours. 666 grams of the process mass were filtered, and the separated productanalyzed as follows:

The remainderof the process mass, 3016 grams,

was blown with CO2 for 25 minutes at 150 C.

A 52 gram increase in Weight of process mass was noted as a result of CO2 treatment. The mass was filtered and the separated product analyzed as follows:

Basic No 10. 25

Per cent sulfate ash 40.9

Metal ratio 8.35

Empirical formula QMa.s5(AO) 0.44(AI) 6.91

Aorns USEFUL IN PREPARATIONOF OILSALTS Since the meaning of the term soap is restricted to salts of carboxylic acids, we utilize the term oilsalt as meaning the oil-soluble alkaline earth metal salts of organic acids. term oilsalts excludes oil-insoluble salts.

The

f -In preparing the organic metal complexes of this invention, the oilsalts or their acid derivatives are used as starting materials. The term starting material as used herein and in our co-pending applications above identified, is defined as oilsalts and their acid derivatives. Thus, barium petroleum sulfonate is an oilsalt, petroleum sulfonic acid is a derivative of this oilsalt, and either one or both can be used as a starting material. At this point it should be noted that whereas earlier workers found it necessary to first prepare a normal oilsalt and then react the oilsalt with an additional amount of a salt-forming material, the process of this invention can be carried on as a one-step process by beginning with the oil-soluble organic acid. While it is possible to first prepare an oilsalt of the organic acid in the usual way, by a conventional salt-forming procedure, and then begin the process by utilizing such oilsalt as one of the starting materials, it may be more convenient to employ as the starting material the organic acid rather than the oilsalt. The process is operable for the production of certain types of compounds when utilizing as starting materials any of the complexes produced by the prior art processes. Also, as a starting material, mixtures of acids and oilsalts can be used to produce the complex. Oilsalts can be prepared from organic acids containin at least 12 aliphatic carbon atoms and selected from the class consisting of aliphatic and cyclic; sulphur acids, carboxylic acids, phosphorus acids, the thio acids of any of the foregoing acids.

More specific examples of organic acids useful in preparation of oilsalts are the sulphur acids including sulphonic, sulphamic, sulphinic, thiosulphonic, etc., and of these the sulphonic acids will find particular application under the present invention. A more specific identification of the sulphonic acids is given hereinbelow.

The carboxylic acids useful in preparation of oilsalts include the fatty acids wherein there are present at least about 12 and preferably 15 carbon atoms, such as, for example, palmitic, stearic, myristic, oleic, linoleic, etc. acids. The carboxylic acids of the aliphatic type can contain elements in the aliphatic radical other than carbon and hydrogen; examples of such acids are the carbamic acids, ricinoleic acids, chlorostearic acids, nitrolauric acids, etc. In addition to the aliphatic carboxylic acids, it is intended to employ the cyclic types such as those containing a benzenoid structure, 1. e., benzene, naphthalene, etc., and an oil-solubilizing radical or radicals having a total of at least about 15 to 18 carbon atoms. Such acids are the oilsoluble aliphatic substituted aromatic acids as for example, stearyl-benzoic acids, monoor polywax substituted benzoic or naphthoic acids wherein the wax group contains at least about 18 carbon atoms, cetyl hydroxy-benzoic acids, etc. The cyclic type of carboxylic acids also includes those acids which have present in the compound a cycloaliphatic. group. Examples of such acids are petroleum naphthenic" acids, cetyl cyclohexane carboxylic acids, di-lauryl deca-hydronaphthalene carboxylic acids, di-octyl cyciopentane carboxylic acids, etc. It is also contemplated to employ the thio-carboxylic acids, that is, those carboxylic acidsin which one or both of the oxygen atoms of the carboxylic group are replaced by sulphur. These carboxylic and thiocarboxylic acids can be represented by the following formulae:

I (Born-0x211 1r R cx2- H wherein R is an aliphatic radical, it is at least 1, and (RT): contains a total of at least about 15 atlases phatic group containing at least 12 carbon atoms 1 wherein X and X are either oxygenor sulphur and at least one X and one Xflis sulphur, and R and R. are each either the same or .difier'ent organic radicals or hydrogemand wherein at least one is an organic radical and at least one B. is hydrogen andwhereinat least one R is an organic radical and, at leastjone Ris hydrogen.

Therefore, such formulae, include the oil-soluble organic thio-acid s.0f phosphorus, more particularly the organic thiophosphoric acids and the organic thiophosphorous acidshrThe organic radicals Rand R .,can, be aliphatic, cycle-aliphatic, aromati c, aliphatim. and cyclo'aliphaticsubstituted aromatic, ,etc. ,The. organic radicals Rand R preferably contain, a totalv of at least about12 carbon atoms in each of the above thioacid types I and II, Examples of, such acids are dicapryl dithiophosphoricacids, ,di-(methyl-cyclohexyl) dithiophosphoric acids, dilauryl dithiophosphoric acids,; ,dicapryl dithiophosphorous acids, di-fimethfl-cyclohexyl) .dithiophosphorous acids, lauryl monothiophosphoric acids, dirOJU- tyl -phenyl) .dithiophosphoric, acids, and mixtures of two or more of the foregoing acids.

, Certain of the abovedescribed thio-acids of phosphorus such as for. example di-capryl dithiophosphoric acid are also commonly referred to as acidesters,

As indicated, our process isv applicable not only when using the oil-soluble organic acid as such as oneof the starting materials, but also oilsalts or the alkaline earth metal salts of such organic acids. The present processwill produce a high metal content organo metallic material when as one of the starting materials one uses any of the metal organic complexes produced by the prior art workers, such as for example, Griesinger, Campbell et al., McLennan and Mertes. We thus may utilize as a starting material the end product produced by these prior art workers and from them produce the a r 28 novel high metal content complex of our in vention.

From the broad class of available organic acid compounds, it is preferred to employ the oilsoluble sulphonic acid compounds. Furthermore, of the available alkaline earth metal salts of organic acids, the barium salts thereof are preferred for the reason that unexpectedly excellent results are obtained by the use thereof. These oil-soluble sulphonic acids, and the alkaline earth metal salts thereof can be represented by the following structural formulae:

In the above formulae M is either an alkaline earth metal, preferably barium, or hydrogen; T is a cyclic nucleus erther of the monog or polynuclear type including benzenoidor heterocyclic nuclei such as benzene, naphthalene, anthracene, phenanthrene, diphenylene, thianthrene, phenothioxine, diphenylene sulphide, diphenylene oxide, diphenyl oxide, diphenyl sulphide, diphenyl amine, etc.; R is an aliphatic. group such as alkyl, alkenyl, alkoxy, alkoxy alkyl, carboalkoxyalkyl, or aralkyl groups, a: is at least 1, and R:

contains a total of at least about 15 to 18 carbon atoms; R, in Formula II is an aliphatic radical containing a total of atl'ea'st about 15 to 18 carbon atoms, and M is either an alkaline earth metal, preferably b'a'riun'i, or hydrogen. When R. is an aliphatic substituted,cycloaliphatic group, the aliphatic substituent should contain a total of at least about 12 carbon atoms. Examples of types of the R. radical are 'alkyl, alkenyl, and alkoxy-alkyl radicals, and aliphatic substituted cycloaliphatic radicals where the aliphatic group is alkyl, alkoxy, alkoxy-alkyl, carboalkoxyalkyl, etc. Specific examples of R are cetyl-cyclohexyl, lauryl-cyclohexyl, ceryloxyethyl, and octadecenyl radicals, and radicals derived from petrolatuin, saturated and unsaturated paraffin wax, poly olefins, including poly- C3, C4, C5, C6, C7, C8, olefin hydrocarbons. The groups T, R and R in the above formulae can also contain other organic or inorganic substituents-in addition to those enumerated above, such as for example, hydroxy, mercapto, halogen, nitro, amino, nitroso,-carboxy, ester, 'etc.

In Formula I above, 11:, andbare-at 'least one; Whereas in Formula -II,-a;d,-and-c are at least one.

The following are specific examples of oil soluble sulphonic acids coming within Formulae I and II above,'and it is to be understood that such examples serve to also illustrate the alkaline earth metal salts of thesulphonic'acids. In other words, for every sulphonic acid, it is intended that the alkaline earth metal salt thereof is also illustrated. This includes "specifically, the barium, strontium, andcalcium'salts of the hereinbelow illustrated'sulphonic acids.

Such sulphonic acids "are mahogany sulphonic acids; petrolatum sulphonic acids; monoand polywax substituted naphthalene sulphonic, phenol sulphonic, diphenyl thersulphonic, di-

, phenyl ether disulphonic, naphthalene disulphide sulphonic, riaphthalenedis ulphide disulphonic, diphenyl amine ldisulphonic, diphenyl amine sulphonic, thiophene :sulphonic, alphachloronaphthalene sulphonic acidsfetcq other substituted sulphonic acids such; as cetyl chloro- H benzene sulphonic acids, cetyl-phenol sulphonic acids, cetyl-phenol disulphide sulphonicacids, cetyl-phenol mono-sulphide sulphonic "acids,

cetoxy capryl-benzene sulphonic acids, di-cetyl thianthrene sulphonic acids, di-lauryl betanaphthol sulphonic acids, and dicapryl nitronaphthalene sulphonic acids; aliphatic sulphonic acidssuch as paraffin wax sulphonic acids, unsaturated parafiin Wax sulphonic acids, hydroxy substituted paraffin wax sulphonic acids, tetraisobutylene sulphonic acids, tetra-amylene sulphonic acids, chloro-substituted parafiin wax sulphonic acids, 'nitroso parafiin wax sulphonic acids, etc.; cycloaliphatic sulphonic acids, such as petroleum naphthene sulphonic acids, cetylcyclopentyl sulphonic acids, lauryl-cyclo-hexyl sulphonic acids, 'bis-(diisobutyl) -cyclohexyl sulphonic acids, monoand poly-wax substituted cyclohexyl sulphonic acids, etc.

With respect to the sulphonic acids, it is intended herein to employ the term petroleum sulphonic acids to cover all sulphonic acids which are derived from petroleum products. Additional examples of sulphonic acids and/or alkaline earth metal salts thereof which can be employed as starting materials are disclosed in the following U. S. patents: 2,174,110; 2,174,506; 2,174,508; 2,193,824; 2,197,800; 2,202,791; 2,212- 786; 2,213,360; 2,228,598; 2,233,676; 2,239,974; 2,263,312; 2,276,090; 2,276,097; 2,315,514; 2,319-

121; 2,321,022; 2,333,568; 2,333,788; 2,335,259; 2,337,552; 2,346,568; 2,366,027; 2,374,193 and 2,383,319.

Of the various types of organic acids and oilsalts thereof enumerated above, i. e. sulphur acids, carboxylic acids, phosphorus acids, etc., it is preferred to employ the sulphur-bearing organic acids or oilsalts thereof. However, it is to be understood that all of organic acids and oilsalts thereof are not equivalent in their ability to complex with unusual amounts of inorganic alkaline earth metal compounds in the presence of aquasalts, because under certain conditions, some organic acids or salts thereof are more effective than others.

MATERIALS USEFUL 1N PREPARATION or ORGANIC AQUASALTS Aquasalts, as previously defined, are oil-insoluble salts. The organic aquasalts and their acid derivatives are effective as promoters and may be so designated, since their function is to promote the formation of the organic metal complexes.

The promoter employed in the process of this invention can be the organic compound (AO)H wherein H is hydrogen or the metal equivalent thereof and (A0) the hydrogen equivalent of the anion of an aquasalt. Also the aquasalt of (AO)H can be usedalone or in admixture with the compound (AO)I-I. The compounds (AO)H should have ionization constants measured in water at 25 C. greater than about 1X10- water 50 pounds which can be employed in forming the .metal complexes in accordance with the present 75- sulphonic acids, beta-naphthol alpha-sulphonic invention, specific examples areenumerated below. It is to be understood that while only the ionizable organic compounds are illustrated, it is intended that the alkaline earth metal salts thereof or the aquasalts are included as specific examples. More specifically, the calcium, barium, and strontium salts of such illustrated ionizable organic compounds are intended.

The term phenolic compound as used in this specification and the appended claims is intended to include all organic compounds having at least one hydroxyl group attached directly to .a benzenoid carbon atom which may be part of a single or fused ring, and which compound may or may not have other substituents on the benzenoid nucleus. It should likewise be understood that a phenol is a sub-class of a phenolic compound, in which there is only a hydroxyl group on the benzene ring or in addition to the hydroxyl group, there is also present in the molecule a single hydrocarbon group or a plurality thereof. Those phenolic compounds containing not more than 30 carbon atoms in the molecule are preferred.

Throughout this specification and in the claims, whenever we use the term enolizable organic compounds we mean those salt-forming compounds Which in the salt-forming state contain a hydroxyl radical linked to an acid-forming element which is either a non-heterocyclic nitrogen atom or a non-benzenoid carbon atom, such acidforming element being bonded to an adjacent carbon atom, said salt-forming compounds being capable of existing in a tautomeric form wherein the hydroxyl radical referred to above may revert to a doubly bonded oxygen atom, i. e., wherein the oxygen atom of said hydroxyl radical may be bonded either as wherein X is nitrogen or a non-benzenoid carbon.

The ionizable organic compounds found useful for preparation of organic aquasalts are phenol; alkylated phenolssuch as, for example, cresols, xylenols, p-ethyl phenol, di-ethyl phenols, npropyl-phenols, di-isopropyl-phenols, p-t-butylphenol, p-t-amyl-phenyl, p-cyclo-pentyl-phenol, p (4 methyl cyclohexyl) phenol, sec-hexylphenol, n-heptyl phenol, diisobutyl phenols, 3,5,5,-tri-methyl-n -hexyl-phenol, and other lowmolecular weight phenols whose alkaline earth metal salts are oil-insoluble; aryl substituted phenols, e g. phenyl phenol, diphenyl phenol, etc.; poly-hydroxy aromatic compounds such as alizarin, quinizarin' or polyhydroxy-benzenes, e. g., hydroquinone, catechol, pyrogallol, etc.; mono-hydroxy naphthalenes, e. g., alpha-naph- 'thol,'beta-naphthol, etc.; polyhydroxy naphthalenes, e. g., naphthohydroquinone, naphthoresorcinol, etc.; the alkylated polyhydroxy-aromatic compounds such as octyl-catechols, triisobutylpyrogallols, etc.; substituted phenols such as pnitro-phenol, picric acid, o-chlorophenol, t-butyl- I chlorophenols, p-nitro-o-chlorophenol, p-aminophenol, etc; lower molecular weight hydroxy aromatic carboxylic acids such as salicylic acid,

chloro-salicylic acids, di-isopropyl-salicylic acids,

I gallic acid, 4-hydroxyl- 1-naphthoic acid, etc lower molecular weight aromatic sulphonic acids suchas p-cresol sulphonic acidap-t-butyl-phenol 3i acid, etc.; lower molecular weight aromatic carboxylic acids such as benzoic acid, p-nitrobenzoic acid, o-chloro-benzoic acid,;p-toluic acid, p-t-butyl-benzoic acid, alpha naphthoic acid, etc.; lower molecular weight aromatic sulphonic acids such as benzene sulphonic acid, p-chlorobenzene sulphonic acid, p-nitrobenzene sulphonic acid, p-tolyl sulphonic acid, p-t-butylbenzene sulphonic acid, t-amyl-naphthalene sulphonic acids, etc; lower molecular weight aliphatic sulphonic acids such as ethyl sulphonic acid, beta-chloro-ethyl sulphonic acid, gamma nitro propyl 'sulphonic acid, octyl sulphonic acids, chloro -diisobutyl sulphonic acids, diisobutenyl sulphonic acids, etc.; nitroparafiins such as l-nitro propane, 2-nitro-n butane, l-nitro-l-(p-diisobutyl phenoxy) pro pane, etc.; and other-enolizable compoundssuch as, for example, oximes, e. g., isophorone oxime, benzal acetone oxime; imines, e. -g., 4-keto-2- pentylidene imine; amides, e. -g., N-buty-l-benzamide, o-chloro-benzamide, acetamide, acetanilide; keto-esters, e. g., ethyl acetoacetate, phenyl acetoaoetate; poly-ketones, e. g., acetylacetone, benzoyl acetone; poly-esters, e. g., di-

ethyl malonate, di-benzyl malonate; imides, etc;

'lower molecular weight acids of-phosphorus including aliphatic dithiophosphoric acids, e. -g., di-isopropyl dithiophosphoric acid, di-n-butyl dithiophosphoric acids, etc.; phosphoric acids, e. g., di-(phenyl) dithiophosphoric acids,-etc., the aliphatic mono-thiophosphoric acids, e. g., diethylmonothiophosphoric acids, etc., the aromatic mono-thiophosphoric acids, e. g., di-tolyl monothiophosphoric acids, di- (isopropyl-phenyl) monothiophosphoric acids; the aliphatic phosphoric acids, e. g., di-ethyl phosphoric acid and di-n-butyl phosphoric acid; the aromatic phosphoric acids, e. g., di-phenyl phosphoric acid and diep-tolyl phosphoric acid; the organic acids of phosphorus containing at least one carbon to phosphorus bond, e. g., dipropyl phosphinic acid, di-ethyl dithiophosphinic acid, n-butyl phosphonic acid, phenyl phosphonic acid, di-phenyl dithiophosphinic acid, etc.; the aliphatic phosphorousacids, -e.-g .,-monon-butyl phosphite, mono-ethyl trithiophosphite, di-ethyl monothiophosphite, etc; the aromatic phosphorous acids, e. g., mono-phenyl phosphite, di-p-tolyl trithiophosphite, etc.

Additional examples of .compounds whichca-n be employed as promoters are given inthefollowing U. S. patents: 2,174,110;. 2,174,111; 2,174,492;

2,174,505; 2,174,506; 2,174,507; 2 ,174,508;'2,174,- 509; 2,202,791; 2,228,598; 2,265,163; "2,276,097; 2,3l9,12l; 2,321,022; 2,3331788; 2,335,259 and 2,337,552.

However, it is to be understoodtl'iat the above enumerated ionizable organic compoundsand the alkaline earth metal saltsthereof or aquasalts are not all equivalent as promoters, but .that under certain conditions some are'rnore effective than others.

THE INITIAL. INORGANIC .AQUAsAL-rUsEo mama Peooirss The salt-forming compounds which are employed to impart to the process massa-ndcomplex the specified amount of metalmay be'broa'd-ly sulphide, hydrosulphide, halide,-hydride; amide, basic carbonate, 'etc. Oftheinorganic alkaline earth metal compounds; good results are obtained aromatic dithio- 32 with those having awater solubility of at least about 0,0003% at 50 C., and preferably at least about 0.006%. Still more preferred are'those inorganic alkaline earth metal compounds, saturated aqueous solutions of which give an alkaline reaction or pH value greater than 7.

To further illustrate the large number and variety of classes of inorganic compounds which can be employed, specific examples thereof are enumerated below.

The alkaline earth metal inorganic compounds include the barium containing compounds such as barium hydroxide, barium oxide, barium sulfide, barium carbonate, barium bi-carbonate, barium hydride, barium amide, barium chloride, barium bromide, barium nitrate, barium sulfate, barium borate, etc.; the calcium containing compounds such ascalcium hydroxide, calciumoxide, calcium sulfide, calcium carbonate, calcium bicarbonate, calcium hydride, calcium amide, calcium chloride, calcium bromide, calcium nitrate, calcium borate, etc,; the strontium-containing compounds such as strontium hydroxide, strontium oxide, strontiumsulfide, strontiumcarbonate, strontium bicarbonate, strontium amide, strontium nitrate, strontium hydride, strontium nitrate, etc. The corresponding basic saltsof the above described compounds are also intended, however, it should be understood that the inorganic alkaline earth metal compounds are not equivalent for the purposes of the present invention,because under certain conditions some are more effective or desirable than others.

Aormo TREATMENT USEFUL FOR Mooirrmc THE lvIETAL COMPLEX (I) QMz(AO)y(OH)a:-| CO2 .QMz,(AjO) ('CO3)+H2O A second function of the acidic treatment is to modify the ratio y the ratio of inorganic. aquasalt (AI) to organic aquasalt (A0) in the complex. vInchanging this ratio, the characterof the inorganic aquasalt present may also be changed as illustrated in the above equation. To illustrate this particular aspect the following equation is presented:

It will be noted that in Formula II-1 y in Formula III-.2

1 c a y b a and therefore,

is greater in Formula II-2.

The particular effect of the acidic treatment depends onthe relation-of the ionization constant of said acidic'reagent with respect to the ionization constants of the acids of (A) and (AI). When the ionization constant of the acidic reagent is greater than the ionization constant of the acid of (AI), but less than the ionization constant of the acid of (AO) the reaction takes place according to Equation I above. For example, the conditions set forth in the Equation I above would prevail in the following specific reaction:

When the ionization constant of the acidic reagent is greater than the acid of (A0) and either greater than or less than the ionization constant of the acid of '(AI), i. e.,non-critical in this latter respect, the equations set forth under (II) above will'occur. For example, this particular set of conditions is realized in the following specific example:

" The metal complexes produced in accordance with the equations given under (II) above have been found to be particularly useful in the preparation of permanently oil-soluble products. In order to give a better understanding of the complicated reactions which may occur therein, the following discussion is presented.

As previously indicated, one form of the process of the present invention includesthe step of treating the immediate complex product with an acidic material for the purpose of liberating from the complex at least a portion of the anion of the material previously referred to as the promoter. A particularly effective acidic material which has been utilized for this purpose is carbon dioxide. We are aware of the fact that the prior art suggested transforming a sodium hydroxidecalcium sulphonate complex into the sodium carbonate-calcium sulphonate complex or the corresponding bicarbonate complex by blowing'the hydroxide complex with carbon dioxide at elevated temperatures.

In our process, the step of treating with an acidic materialsuch as carbon dioxide or air has the effect of freeing from the immediate complex product formed at least a portion of the anion of the promoter used. The nature of the product formed by regenerating from the immediate end product a portion of the anion of the promoter material leaves that complex with a composition which is quite different from the other prior art metal organic complexes previously produced. It

is recognized that in accordance with the present invention, the alkaline earth metal salt of the ionizable organic compound can be employed as thepromoter in forming the salt complex. However, when such a salt is used as the promoter and the resulting complex is treated with an acidic material, a portion of the anion of the organic compound is freed from its salt. The acid treating step referred to in this paragraph is represented by Formula II above.

For the purpose of releasing from the complex a portion of the anion of the ionizable organic compound used as a promoter, an important feature or characteristic of the acidic material is that it must, when present in the mass containing 34 liquid or a gas. The liquids can include the strong or weak acids, such as, for example, hydrochloric,

sulphuric, nitric, carbonic acids, etc., whereas the 7 gas is for the most part an anhydride of an acid or an acid anhydride gas.

' The followingare additional specific examples of acidic materials, viz.: I-ICl, S02, S03, CO2, air (considered acidic because of CO2 content), N02, HzS, N203, PCh, SOClz, C102, HzSe, BF3, CS2, COS, etc.

Preferably the inorganic aquasalt is selected from the class consisting of the alkaline earth metal derivatives of carbonic acid, water, sulfurous acid, dithiocarbonic acid, and sulfuric acid.

It is to be understood, however, that all acidic materials are not equivalent for the purposes of the present invention, but that under certain conditions, some are more effective or desirable than others.

The complex of the present invention can be produced by using the same alkaline earth metal in the oilsalt promoter and inorganic compound; or such complexes can be derived from components containing dissimilar alkaline earth metals.

In some instances it is desirable to employ a mixture of oilsalts which contain at least two or three dissimilar alkaline earth metals; or the same distribution of metals can be obtained by varying the typeof promoter and/or inorganic compound in various combinations with the oilsalt. It is therefore possible to employ various combinations of dissimilar alkaline earth metals in the starting materials used in preparing the complex product.

From the numerous examples given above as specific embodiments of the various processes and complexes of our invention it will be observel that four principal processes have been illustrated by which the several complexes may be produced. a The first of such processes, as represented by Examples 1, 3-10, 12, 14-22, 34-37, 41-43, 45, 46, 49, 52, 53, and 56 comprises the reaction of an oilsalt and compounds which form the aquasalts. 4

The second method, as represented by Examples 47, 48, 50, 51 and 54, utilizes the additional step of reacting the filtered end product of the first process, with an acidic material. The acidic material may have the eifect, as stated above, of

1 replacing part of the anion of the organic aquasalt from the complex without any substantial change in the metal ratio of the complex. The liberation of such anion by this step of acid treatment may be followed by a recovery, as by distillation, of the organic salt forming compound corresponding to the anion of the organic aquasalt.

In the third method, represented by Examples 11, 13, 23-33, 33-40, 44, 5'7 and 58, the complex formed by the first named process is treated with an acidic material prior to filtration, i. e. in the presence of uncomb-ined inorganic metal com.- pound present in the process mass. When following the procedure of this third method, at least some of the organic aquasalt remains unconverted in the complex.- Any or all of the anion the complex, possess an ionization constant higher than the ionizable organic compound used as the promoter or used in forming the organic aqua-salt.

The acidic material usually employed is a 26-29, 31. 33 and 56, comprises reacting a complex of an oilsalt; an organic aquasalt of a relatively strong organic salt forming compound and an inorganic aquasalt of a relatively weak salt forming compound with an acidic material of such strength that it will react with a salt forming compound from which the inorganic aquasalt was formed whereby the'latter is modified by the acid treating step whereas the relatively stronger organic aquasalt remains unaffected.

PROCESS CONDITIONS When carrying out the first of the four diiferent processes outlined above, the salt complex is prepared by combining the reactants in the presence of water. The water can be present as a result of addition thereof to the mixture, or liberated from either the essential components or other additionally present compounds as a result of being subjected to heat.- However, it is preferred to add water to the mixture to effect salt complex formation. It has been found that the metal complex can be prepared when using small quantities of water such as about 1 mole of water per mole of inorganic metal compound. However, more usually about 5 to 50, and preferably about to 30, moles of water per mole of inorganic metal compound are used.

Generally the complex formed with the inorganic alkaline earth metal compound, the oilsoluble organic acid or the alkaline earth metal salt thereof, and the promoter is prepared by heating the components in the presence of water at a superatmospheric temperature while insuring thorough mixing and then still further heating said mixture to subtantially remove all of the water. At least five variations of the previously outlined four processes are available by which the complex can be formed, namely:

(a) The promoter is added to the oilsalt, followed by addition of an aqueous solution or suspension of the initial inorganic aquasalt; the mixture is held at a superatmospheric temperature for a reasonable length of time while efiecting thorough mixing, and then the total mixture is further heated to remove substantially all water which might be present;

-(b) The initial inorganic aquasalt in a dry state is added to a mixture of oilsalt or thecorresponding acid thereof, promoter and water heating while insuring thorough mixing, and then further heating to remove substantially all of the water;

(c) The acid of the desired oilsalt is mixed with the promoter, then an aqueous solution or suspensionof the inorganic alkaline earth metal compound is added thereto, the mixture is heated andagitated at a superatmospheric temperature for a time sufficient to insure thorough mixing, and followed by subjecting the total mixture to dehydration conditions in order to remove substantially all of the water;

(d) In any of. the methods discussed herein for preparing the metal complex, a substantial increase in metal content is usually effected by treating the mass containing the complex prodnot with an acidic material just after substantial amounts of water are driven ofi and just before the mass is filtered.

(e) The sediment formed from any of the aforementioned methods can be employed either alone or with additional promoter in any of the methods given above.

The conditions to be observed in carrying out the remainder of the four processes, above identi- 36 fled, will be self-evident from the processes themselves and the specific examples which have been indicated representative of such processes.

In all of the methods described above for preparing the metal complex, the step of removing substantially all of the water which is present is accomplished at a temperature not substantially in excess of 350 0., perferably about C. to 200 C. The technique employed to remove the water includes, for example, a conventional flash stripping operation which involves passing the material in a thin film state over a large heated area of glass, ceramic, or metal; heating under sub-atmosphericpres-sure as well as heating un der either atmospheric or superatmospheric pressure. At a later stage, the acidic material when used in gaseous form, may be used to remove the last portion of water. It can therefore be seen that the temperature as well as the time for effecting substantial removal of water will vary considerably depending on the amount of material being processed'and on the technique employed therefor. Generally, the time required to effect substantial removal of water is at least about 15 minutes or less and can be as high as 10-15 hours or more. Usually, however, it is most-convenient to employ atmospheric pressure for such an operation, and consequently it requires about 1 to 5 hours to remove substantially all of the water from the process mixture. It was observed that satisfactory metal complexes are obtained when using any of the techniques described above, and that the final water content can be up to about 2% or more.

Usually, as indicated above, the components are combined and agitated at an elevated temperature to insure thorough mixing, and then water is removed therefrom. It should be understood that the process to form the metal complex can be effected without the preliminary heating and mixing period, if desired. It is therefore not essential to this invention to have such a preliminary step because all that appears necessary is to mix the components and remove substantially any water which is present.

RELATIONSHIPS BETWEEN THE VARIOUS AMOUNTS or THE SEVERAL COMPONENTS IN THE COMPLEX For the purposes of this specification and the appended claims, the relative amounts of starting material (oil-soluble organic acid or the alkaline earth metal salt thereof) and promoter is expressed in the ratio of equivalents of the latter to the former. In accordance therewith, the ratio of equivalents of promoter to start n material is broadly from about 0.01 to 10, more usually from about 0.02 to 5.0, and preferably from about 0.05 to 3.0.

It will be observed that the complexes of this invention comprise in chemical combination the following:

or oilsalt-Organic Aquasalt-Inorganic Aquasalt with the total metal (M) present attaches to the anions of each of such salts.

On this basis, y should be from .01 to 10 and more desirably from .02 to 5.0 and preferably from .05 to 3.0.

a: is always greater than y. When 1/ is less than 1, then a: should be at least 1.5g. When 1/ is one or more, then a: should be equal to at least y+.5. In most instances,

for one hour. blown through the mixture at 150 C. for

should-be equal to 1.5.and preferably at least 4.0. As indicated above, metal (same or different) will be combined in each of the three salts. The ratio of the total metal present to the metal present in the oilsalt is referred to for convenience as the metal ratio. All of the complexes of this invention are characterized by a metal ratio greater than 1 with best results secured when such metal ratio is above 4.

When a complex is formed which has ratios of the type referred to above which lie outside of the values given, such complexes will be found undesirable 'for various reasons. In most cases, complexes which have ratios falling outside of the values given will be oil insoluble or unusable for the purposes. Experimental data which establishes as critical the values for the several ratios given above is demonstrated by the following examples: T

EXAMPLE 63 A mixture of 343 grams of petroleum sulfonic acid and grams of mineral oil was heated to C. then treated with a mixture of 64 grams of barium hydroxide, 94 grams of water and 21.4 grams of acetic acid (ratio of equivalents of inorganic aquasalt to organic aquasalt, 0.03). One thousand grams of mineral oil was added and the mixture was heated at 95-120 C. for, two hours, then dried at 150 C. a The reaction mixture was cooled to 95, 16 grams of water was added, and the mixture was dried again at 150 C. The product was oil-insoluble and grease-like in con sistency.

EXAlVPLE 64 of water was added and this mixture was dried again at 150 C. The product was oil-insoluble andgrease-like in consistency.

. EXAMPLE 65 A mixture of 1530 grams of a 30% oil solution of barium petroleum sulfonate having a 7.6%

sulfate ash, 35.3 grams of acetic acid, 270

grams of barium oxide (sufiici-ent to make the ratio of equivalents of inorganic aqu'as'alt to organic aquasalt equal to at least 3.5 in the end product) and 220 grams of water wa's heated at -105 C. for one hour, then at- C. A stream of carbon dioxide was minutes, at which point the mixture was substantially neutral. The product mixture was filtered, yielding oil-soluble, viscous liquid, possessing the following properties:

Basic No 0.49

Per cent sulfate ash 24.25

Metal ratio 3.96

Empirical formula Qmss (A0) 0.59 (AI) 2.3?

As indicated in the section entitled "Acidic Treatment Useful for Modifying the Metal Complex, treatment of the salt complex with an acidic material is done in instances where it is desired to change the character of the total aquaganic acid.

saltpresent in the complex and/or alter the ratio of inorganic aquasalt to organic aquasalt. This treatment is effected at a temperature of from about 25 to 250 C., preferably from about 50 to C. and usually employing from about 0.5 to 20% of acidic material, based on thewelght of metal complex. The time of treatment with the acidic material can vary considerably depending on the desired result. As would be expected, short periods of treatment may cause only partial liberation or release of ionizable organic compound or small decreases in the basic number of the metal complex. However, in general, periods of treatment will range frojmfabout 0.25 to 30 hours or more. In most cases, and particularly where it is desired to recover the promoter, the amount of acidic material used should be at least equivalent to the amount of metal present as the salt of the ionizable form ofpromoter. It isto be understood, of course, that the libertaion of the promoter from its salt can only takeplace when the acidic reagent has a higher ionization constant in the process mass than-the salt-"forming compound of the organic aquasalt.

To substantially increase the metal content of the salt complex, it may be desirable to treat the total mass with an acidic material just prior to filtering same. This treatment may conveniently be effected at a temperature of from about 25 to 250 C. preferably from about 50 to 170 C., using from about 0.5 to 20% of acidic material, based on the total mass, and for a period of from about 0.25 to 30 hours. The acidic material employed is preferably an acid anhydride gas; as defined hereinabove. Treatment'with the acid anhydride gas may be accelerated by superatmospheric pressure. V I

As indicated'above, in order to facilitate an understanding of the amount of metal which can be present in the salt complex, the metalratio is defined as the ratio of the total metal in the salt complex to the amount of metal which is in the form of a normal salt of the oil-soluble or- In accordance therewith, the" salt complex as of this invention will have metal ratios greater'than 1 and up to 9 or more, preferably from about 2 to 8. As for the finished salt complex which is treated after filtration with an l acidic material, the metal content is'substan'tial as a possible explanation of how the metal is held within the metal complex. It is to be understood,

however, that such theory is advanced for the purpose of offering explanations, and is not to be construed as a limitation on the scope of the present invention.

In the following equations, AO represents one hydrogen equivalent of the anion of an organic" aquasalt and, M represents an alkaline earth metal.

For example, in the case of the neutralsul phonate, the charges are distributed as follows:

The electron octets around the two oxygen 1* atoms which are not attached to a metal atom give to each of these atoms a unit negative charge, thus leaving the sulphur atom with a double positive charge.

When the sulphonate, excess inorganicmetal compound, promoter, .and water are reacted according to the present invention, a basic salt (AO)-M-OH is presumed to be formed. This normally oil-insoluble salt dissolves in the reaction mixture because of the electronic attracting force known as a hydrogen bonding.

Initially the following reactions may occur:

According to this electronic explanation, the (AO) anion of the aquasalt (AO)M-OH appears to function as a carrier for the M(OH) 2, and thus facilitating the communicating of the M(OH)2 into close positions with the negatively charged oxygen atoms of the sulfonate radical.

It will be noted that the above theoretical structures can be represented by the empirical mula: QMz(AO)1 (AI)I and in the last theoretical structure shown: Q=RSO3;

(AO)=one hydrogen equivalent of the anion of at least one organic aquasalt, for example, C'eI-I50; C4H9C6H50, etc.;

(AI)=one hydrogen equivalent of the anion of at least one inorganic aquasalt, for example, OH, -O-, etc.

It will be readily appreciated that z, y, and a: may often be non-integral values in the actual practice of the invention, since the finished metal complex material may and, in fact, usually does comprise a mixture of two or more of the above structures.

Having thus described the present invention by furnishing specific examples thereof, it is to be understood that no undue limitations or restrictions are to be imposed by reason thereof, but that the scope of this invention is defined by the appended claims.

The salt complexes produced in accordance with the present invention can be employed in lubricants including oils and greases, and for such purposes as in crankcases, transmissions, gears, etc. as well as in torque converter oils. Other suitable uses for such complexes ar in asphalt emulsions, insecticidal compositions, fire-proofing and stabilizing agents in plasticizers and plastics, paint driers, rust inhibiting compositions, pesticides, foaming compositions, cutting oils, metal-drawing compositions, flushing oils, textile treatment compositions, tanning assistants, metal cleaning compositions, emulsifying agents, antiseptic cleansing compositions, penetrating agents, gum solvent compositions, fat splitting agents, bonding agent for ceramics and asbestos, asphalt improving agents, flotation agents, improvin agents for hydrocarbon fuels such as e. g., gasolene and fuel oil, etc.

More particularly, the complexes of this invention are especially adapted for the preparation of lubricants, paint driers and plastics, particularly the halogen bearing plastics. In these respects, the salt complex can be employed in the following concentrations based upon the weight of the total composition.

Broad Usual Preferred Range Range Range Percent Percent Percent Lubricant '0. 01-20 0. 2-15 0. 5-10 Stabilizing Agent for Plastimum 0. 05- 5 0.1- 3 0. 2- 2 Pamt Duet 0. 2-25 i 0. 5-20 1. 0-15 LUBRICANT CONTAINING ORGANIC METAL COMPLEXES While the metal complexes of the present invention are useful per se as improving agents for lubricating greases and oils, especially mineral lubricating oils intended for use in the crankcases of internal combustion engines, they are most advantageously employed in combination with one or more additional improving agents of the prior art such as, for example, the numerous prior art oxidation inhibitors, detergents, extreme pressure agents, rust inhibitors, and oiliness agents.

In addition to the above-named types of cooperating improving agents, the present invention also contemplates the inclusion, in the finished lubricant, of materials intended to modify the physical characteristics of the mineral lubricating oil base. Examples of such materials are foam inhibitors, pour point depres- 

1. AS A NEW COMPOSITION OF MATTER AN OILSOLUBLE, ORGANIC, ALKALINE EARTH METAL COMPLEX HAVING THE EMPIRICAL FORMULA: 